EP0910603A1 - Melanges-maitres et procedes de preparation desdits melanges - Google Patents
Melanges-maitres et procedes de preparation desdits melangesInfo
- Publication number
- EP0910603A1 EP0910603A1 EP97926196A EP97926196A EP0910603A1 EP 0910603 A1 EP0910603 A1 EP 0910603A1 EP 97926196 A EP97926196 A EP 97926196A EP 97926196 A EP97926196 A EP 97926196A EP 0910603 A1 EP0910603 A1 EP 0910603A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- carrier
- additive
- masterbatch
- chain length
- acids
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/20—Compounding polymers with additives, e.g. colouring
- C08J3/22—Compounding polymers with additives, e.g. colouring using masterbatch techniques
- C08J3/226—Compounding polymers with additives, e.g. colouring using masterbatch techniques using a polymer as a carrier
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/20—Compounding polymers with additives, e.g. colouring
- C08J3/203—Solid polymers with solid and/or liquid additives
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B67/00—Influencing the physical, e.g. the dyeing or printing properties of dyestuffs without chemical reactions, e.g. by treating with solvents grinding or grinding assistants, coating of pigments or dyes; Process features in the making of dyestuff preparations; Dyestuff preparations of a special physical nature, e.g. tablets, films
- C09B67/0071—Process features in the making of dyestuff preparations; Dehydrating agents; Dispersing agents; Dustfree compositions
- C09B67/0092—Dyes in solid form
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2467/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
Definitions
- This invention relates to solid masterbatches.
- the traditional solid masterbatch comprises a high concentration of additives such as coloring substances (dyestuff or pigment) and processing or functional substances (stabilizer, flame retardant, etc.) in a solid carrier which is typically a polymeric material, a waxy product or a mixture thereof.
- the additive is homogeneously dispersed throughout the carrier, typically by melting the carrier, incorporating the additive therein and applying sufficient shear stress to the additive aggregates (pigment as delivered is invariably in aggregate form) in order to reduce them to primary particles. This is followed by solidifying, grinding or pelletizing.
- the shear stress in the molten carrier is generally applied by means of special continuous or batch kneading equipment, most commonly by extrusion. These are by nature high energy processes and the energy is generally proportional to the additive concentration and the dispersion quality of the masterbatch.
- the unique feature of this invention is that an excellent product which has a performance at least equal to that of the best of the known masterbatches can be made by a process which is very easy and energy-efficient to perform.
- Any apparatus which is capable of simple mixing of the ingredients may be used; such apparatus are well known to the art and a suitable apparatus may readily be selected.
- the apparatus may have provision for heating and/or cooling in order to maintain the temperature of the mixture at an appropriate level. It often happens that friction between particles as a result of the act of mixing alone generates sufficient heat to raise the temperature to an appropriate level; indeed, it might in some cases be necessary to cool in order to keep the temperature below the melting point of the carrier. Alternatively, the speed of mixing can be lowered to avoid melting of the carrier.
- the design of the mixing apparatus is, as previously stated, not narrowly critical to the working of the invention.
- features such as size and shape of vessel, impeller design and so on may be selected according to the normal practices and know-how of the art. It is recognized that a particular configuration of mixer which is optimal for one particular mixture may not be optimal for another mixture, but the selection of a suitable configuration is well within the skill of the art in every case.
- agglomerates composite particulates in which individual additive particles are held together by carrier particles.
- the nature of the process means that, unlike known processes where a carrier is completely melted and an additive uniformly dispersed therein, giving rise to a material which comprises additive particles completely encased in carrier, the additive particles are held together by carrier particles which have essentially retained their individual integrity and which therefore do not necessarily (and in most cases do not) completely encapsulate the additive particles.
- additive in aggregate form the additive aggregates are broken up into individual particles by the stirring + the action of the carrier; and (ii) the softened carrier particles adhere to the additive particles, holding them together in agglomerates.
- the masterbatch thus produced is dust-free, has excellent color strength and dispersibility as well as compatibility with a large range of polymeric materials. Moreover, it may contain up to 85% by weight of additive.
- the excellent granulometry obtained by the control of the temperature, the abso ⁇ tion of energy and the speed of the impeller during the process, is important to allow accurate and automatic dosage of the masterbatch during its application.
- the obtained masterbatches have a well defined granulometry in that 90-95% of the agglomerates have a particle size between 75 and 1500 microns. In most cases, the particle size distribution of the final product, even in industrial application, corresponds to the typical curve of Figure 1 and the average particle size is around 300 microns.
- the invention therefore also provides a particulate masterbatch which comprises an additive and a carrier, wherein the masterbatch particles are agglomerates of additive particles and carrier particles, the additive particles being segregated from each other and held together by carrier particles.
- the additives are selected from any suitable solid colorants, typically an inorganic pigment, an organic pigment and/or a dyestuff, antioxidants, heat and light stabilizers, flame retardants, antiblocking agents, antimicrobials, blowing agents, photo- and biodegradants and any other additive which is usually provided in the form of masterbatch for plastics.
- suitable solid colorants typically an inorganic pigment, an organic pigment and/or a dyestuff, antioxidants, heat and light stabilizers, flame retardants, antiblocking agents, antimicrobials, blowing agents, photo- and biodegradants and any other additive which is usually provided in the form of masterbatch for plastics.
- Preferred colorants for use in a masterbatch composition according to the invention are selected from the dyestuffs
- a carrier for use in this invention may be selected from at least one of the materials in the following list
- metal soaps of linear, branched or hydroxylated monocarboxylic acids with C 12 to C 30 chain length ii) long chain fatty acids and other carboxylic acids iii) fatty amides
- mixed polyesters obtained by condensation of a polyol having 2 to 6 hydroxy groups with monocarboxylic acids having Cj 2 to C 30 chain length and aliphatic dicarboxylic acids, and v) esters of linear, branched or hydroxylated monocarboxylic acids having C ]2 to C 30 chain length with alcohols having C 12 to C 30 chain length or polyols with 2 to 6 hydroxy groups
- Typical materials include a polyester produced from glycerol or pentaerythritol, adipic and stearic or octadecanoic acid or an ester produced from glycerol or pentaerythritol and stearic, octadecanoic or hydroxystearic acid.
- group “iv” or “v” materials in combination with another one of the materials in the list.
- a particularly good combination is the combination of group “iv” or “v” material with group “i” in the proportion of 1 part of metal soap to 3 parts of polyester or ester.
- Preferred metal soaps are magnesium or calcium stearate, hydroxystearate, octadecanoate or behenate.
- Preferred fatty acids and other carboxylic acids include stearic, behenic, oleic and montanic acid, as well as hydroxy derivatives of these acids.
- the carrier has a melting point between 40 and 150°C, more preferably between 40 and 120°C.
- the amount of additive present is preferably 30-85%, more preferably 40-80% and the amount of carrier present is preferably 70- 15%, more preferably 60-20%, all percentages being by weight.
- organic pigments it is possible to obtain very concentrated masterbatches containing up to 70% by weight of organic pigment.
- the masterbatches of the invention are substantially dust-free and have good dispersibility in polymeric material which is illustrated by low values in the so-called filter test.
- This test is performed by extruding a granulated blend of masterbatch (17.5% of organic pigment resp. 25% of inorganic pigment in LDPE with MFI 70) with neutral resin through a filter packet with 80/325/80 mesh ASTM and measuring the pressure increase.
- the present invention also avoids the need to extrude or knead the mixture to form a masterbatch and thereby provides good mixability in polymeric material to which it is applied.
- a polymer composition containing polymeric material and 0.05 to 3% (preferably 0.1 to 1%) based on the weight of the polymeric material present of a composition according to the invention. For specific applications concentrations of up to 15% by weight can be possible.
- the masterbatches according to the invention are suitable for inco ⁇ orating additive to any polymeric material, with which solid masterbatches may be used, typical examples being ABS, acetal, acrylic, acrylonitrile, allyl, cellulosic, chlorinated PE, epoxy, epoxy-polyester, ethylene- vinyl alcohol (EVOH), fluoroplastics, ketones, melamine formaldehyde, melamine phenolic, phenolic, polyamide, polyamide-imide, polybutadiene, polybutylene, polycarbonate, polyester, polyetherimide, polyethylene and ethylene copolymers, polyimide, polyphenylene oxide, polyphenylene sulfide, polyphthalamide (PPA), polypropylene, polystyrene and styrene copolymers, polyurethane, PVDC copolymers, sulfone polymers, thermoplastic elastomers, vinyl polymers and copolymers.
- ABS acetal, acrylic, acrylonitrile,
- the masterbatches according to the invention have a good compatibility with a large range of polymeric materials and work especially well with polyolefines, vinyl polymers and copolymers as well as polyacetals, polyesters, polycarbonates, styrenic polymers and copolymers, polyurethanes, polyamides, cellulose acetates and thermoplastic rubber.
- CI Pigment Red 48:2 3.5 kg of CI Pigment Red 48:2 is mixed in a high speed mixer with 0.175 kg of calcium stearate and 3.325 kg of a mixture containing 25% of calcium octadecanoate and 75% of a polyester obtained from 16 moles stearic acid, 7 moles pentaerythritol and 6 moles adipic acid. After 12 minutes, agglomeration is completed at a final temperature of 51° and the product obtained is free flowing and dust free with high dispersion characteristics and high color strength in the majority of polymers.
- CI Solvent Blue 104 2.0 kg is mixed in a high speed mixer with 0.5 kg of an ester obtained from 1 mole glycerol and 3 moles 12-hydroxystearic acid. After 22 minutes, agglomeration is completed at a final temperature of 56° and the product obtained is free flowing and dust free, easily dispersible in polystyrene, engineering and high performance polymers.
- EXAMPLE 3 2.4 kg of CI Iron Oxide Red 1101 is mixed in a high speed mixer with 0.09 kg of calcium stearate and 0.51 kg of the mixture used in Example 1. After 16 minutes, agglomeration is completed at a final temperature of 48° and the product is free flowing and dust free, easily dispersible in the majority of polymers.
- EXAMPLE 4 2.4 kg of CI Iron Oxide Red 1101 is mixed in a high speed mixer with 0.09 kg of calcium stearate and 0.51 kg of the mixture used in Example 1. After 16 minutes, agglomeration is completed at a final temperature of 48° and the product is free flowing and dust free, easily dispersible in the majority of polymers.
- 1 kg of CI Pigment Blue 15:3 is mixed in a high speed mixer with 0.075 kg of calcium stearate and 1.425 kg of a mixture containing 25% of calcium behenate and 75% of a polyester obtained from 7 moles pentaerythritol, 6 moles adipic acid and 16 moles stearic acid. After 13 minutes and 20 seconds, agglomeration is completed at a final temperature of 54° and the product obtained is free flowing and dust free, with high dispersion characteristics and high color strength when it is used in mass coloration of plastics.
- CI Pigment Blue 29 1.5 kg is mixed in a high speed mixer with 0.5 kg of an ester obtained from 1 mole glycerol and 3 moles 12-hydroxystearic acid. After 15 minutes, agglomeration is completed at a final temperature of 56° and the product obtained is free flowing and dust free, easily dispersible in the majority of plastics.
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Processes Of Treating Macromolecular Substances (AREA)
Abstract
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
GBGB9614510.7A GB9614510D0 (en) | 1996-07-10 | 1996-07-10 | Improvements in or relating to organic compositions |
GB9614510 | 1996-07-10 | ||
PCT/IB1997/000818 WO1998001498A1 (fr) | 1996-07-10 | 1997-07-03 | Melanges-maitres et procedes de preparation desdits melanges |
Publications (2)
Publication Number | Publication Date |
---|---|
EP0910603A1 true EP0910603A1 (fr) | 1999-04-28 |
EP0910603B1 EP0910603B1 (fr) | 2004-12-29 |
Family
ID=10796694
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP97926196A Expired - Lifetime EP0910603B1 (fr) | 1996-07-10 | 1997-07-03 | Melanges-maitres et procedes de preparation desdits melanges |
Country Status (6)
Country | Link |
---|---|
EP (1) | EP0910603B1 (fr) |
DE (1) | DE69732111T2 (fr) |
ES (1) | ES2234019T3 (fr) |
GB (1) | GB9614510D0 (fr) |
TW (1) | TW401436B (fr) |
WO (1) | WO1998001498A1 (fr) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE112017005419T5 (de) | 2016-10-28 | 2019-07-18 | Giovanni Broggi | Universelle Pigmentpräparationen zum Färben und Verstärken von Kunststoffen |
Families Citing this family (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB2364260A (en) * | 2000-06-30 | 2002-01-23 | Great Lakes Chemical Corp | Flame retardant dispersible powders on a wax,polymer or organic carrier |
US10472471B2 (en) | 2015-03-10 | 2019-11-12 | Einar A/S | Masterbatch comprising colorant particles and a polyol poly(hydroxy fatty acid) ester as dispersing agent |
DE102017131437A1 (de) | 2017-12-29 | 2019-07-04 | Heubach Gmbh | Verwendung einer Pigmentpräparation zur Herstellung von Lackfarben sowie die danach hergestellte Lackfarbe |
Family Cites Families (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
FR1534058A (fr) * | 1967-06-15 | 1968-07-26 | Aquitaine Petrole | Procédé de mélange d'un agent gonflant aux matières plastiques et produit ainsi obtenu |
US3778288A (en) * | 1971-11-15 | 1973-12-11 | Coal Oil And Gas Corp Ltd | Methods for preparing master batches of additive concentrates |
EP0008083A1 (fr) * | 1978-08-15 | 1980-02-20 | Ciba-Geigy Ag | Procédé de préparation de granulés d'additifs fondant difficilement pour des matières plastiques, en particulier de pigments, par une granulation thermique par rotation, et les granulés ainsi obtenus |
DE3150012A1 (de) * | 1981-12-17 | 1983-06-23 | Basf Farben + Fasern Ag, 2000 Hamburg | "verfahren zur herstellung von staubfreien, rieselfaeigen faerbemitteln" |
DE3637770A1 (de) * | 1986-11-06 | 1988-05-11 | Henkel Kgaa | Staubfreie farbpigmentzusammensetzung fuer kunststoffe und verfahren zu deren herstellung |
NL8701051A (nl) * | 1987-05-04 | 1988-12-01 | Holland Colours Apeldoorn Bv | Gekleurd kunststofgranulaat, werkwijze voor het kleuren van kunststofgranulaat werkwijze voor het vervaardigen van een gekleurd kunststofvoorwerp en inrichting voor toepassen van de werkwijze. |
CA1332198C (fr) * | 1988-01-28 | 1994-09-27 | Warren Baker | Concentres de couleurs |
-
1996
- 1996-07-10 GB GBGB9614510.7A patent/GB9614510D0/en active Pending
- 1996-10-23 TW TW85112980A patent/TW401436B/zh not_active IP Right Cessation
-
1997
- 1997-07-03 WO PCT/IB1997/000818 patent/WO1998001498A1/fr active IP Right Grant
- 1997-07-03 ES ES97926196T patent/ES2234019T3/es not_active Expired - Lifetime
- 1997-07-03 DE DE69732111T patent/DE69732111T2/de not_active Expired - Lifetime
- 1997-07-03 EP EP97926196A patent/EP0910603B1/fr not_active Expired - Lifetime
Non-Patent Citations (1)
Title |
---|
See references of WO9801498A1 * |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE112017005419T5 (de) | 2016-10-28 | 2019-07-18 | Giovanni Broggi | Universelle Pigmentpräparationen zum Färben und Verstärken von Kunststoffen |
Also Published As
Publication number | Publication date |
---|---|
GB9614510D0 (en) | 1996-09-04 |
DE69732111D1 (de) | 2005-02-03 |
WO1998001498A1 (fr) | 1998-01-15 |
TW401436B (en) | 2000-08-11 |
EP0910603B1 (fr) | 2004-12-29 |
DE69732111T2 (de) | 2005-12-22 |
ES2234019T3 (es) | 2005-06-16 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CA2037603C (fr) | Methode de production de pastilles de concentre de matiere colorante | |
US5846607A (en) | Process for producing customized thermoplastic resins | |
US6312639B1 (en) | Processing aid for thermoplastic resin compositions | |
US5604279A (en) | Colorant preparation for producing masterbatches | |
US12012496B2 (en) | Method for the manufacture of a colored polymer composition | |
US5919530A (en) | Process for producing customized thermoplastic resins | |
JP2020517756A (ja) | プラスチックの着色および強化のための万能的な色素製剤 | |
CN107286466A (zh) | 一种含纳米色粉的聚丙烯色母粒及其制备方法 | |
US4076667A (en) | Granules and pellets for the modification of polycondensates which can be shaped, as well as the process for obtaining these granules and pellets and shaped articles thus obtained | |
US10472471B2 (en) | Masterbatch comprising colorant particles and a polyol poly(hydroxy fatty acid) ester as dispersing agent | |
EP0910603B1 (fr) | Melanges-maitres et procedes de preparation desdits melanges | |
EP2173793B1 (fr) | Procédé de préparation d'un mélange maître | |
JPS5934738B2 (ja) | 粒状顔料 | |
JPH11148020A (ja) | 熱可塑性樹脂用着色剤組成物 | |
DE19644718C2 (de) | Verfahren zur Herstellung von pigmentierten oder füllstoffhaltigen Formkörpern | |
JP2001002862A (ja) | ペレット状着色剤とその製造方法および成形品 | |
CN117165071A (zh) | 一种高强度尼龙双6工程塑料制备方法 | |
EP0889076A1 (fr) | Procédé amélioré pour la fabrication de matières thermoplastiques personnalisées | |
MXPA98002504A (en) | Improved process to produce thermoplastic resins manufactured according to specification | |
MXPA98002269A (en) | Improved process to produce thermoplastic resins manufactured according to specification | |
EP0889073A1 (fr) | Procédé amélioré pour la fabrication de matières thermoplastiques personnalisées | |
PL142969B1 (en) | Method of obtaining pigment preparations for colouring synthetic polymers in bulk | |
MXPA98003517A (en) | Improved process to produce thermoplastic resins manufactured according to specification | |
EP0889075A1 (fr) | Procédé amélioré pour la fabrication de matières thermoplastiques personnalisées |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PUAI | Public reference made under article 153(3) epc to a published international application that has entered the european phase |
Free format text: ORIGINAL CODE: 0009012 |
|
17P | Request for examination filed |
Effective date: 19981221 |
|
AK | Designated contracting states |
Kind code of ref document: A1 Designated state(s): BE CH DE ES FR GB IT LI |
|
17Q | First examination report despatched |
Effective date: 19990908 |
|
GRAP | Despatch of communication of intention to grant a patent |
Free format text: ORIGINAL CODE: EPIDOSNIGR1 |
|
GRAS | Grant fee paid |
Free format text: ORIGINAL CODE: EPIDOSNIGR3 |
|
GRAA | (expected) grant |
Free format text: ORIGINAL CODE: 0009210 |
|
AK | Designated contracting states |
Kind code of ref document: B1 Designated state(s): BE CH DE ES FR GB IT LI |
|
REG | Reference to a national code |
Ref country code: GB Ref legal event code: FG4D |
|
REG | Reference to a national code |
Ref country code: CH Ref legal event code: EP |
|
REG | Reference to a national code |
Ref country code: CH Ref legal event code: NV Representative=s name: CLARIANT INTERNATIONAL LTD. |
|
REF | Corresponds to: |
Ref document number: 69732111 Country of ref document: DE Date of ref document: 20050203 Kind code of ref document: P |
|
REG | Reference to a national code |
Ref country code: ES Ref legal event code: FG2A Ref document number: 2234019 Country of ref document: ES Kind code of ref document: T3 |
|
ET | Fr: translation filed | ||
PLBE | No opposition filed within time limit |
Free format text: ORIGINAL CODE: 0009261 |
|
STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT |
|
26N | No opposition filed |
Effective date: 20050930 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: CH Payment date: 20080623 Year of fee payment: 12 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: BE Payment date: 20080613 Year of fee payment: 12 |
|
BERE | Be: lapsed |
Owner name: *CLARIANT FINANCE (BVI) LTD Effective date: 20090731 |
|
REG | Reference to a national code |
Ref country code: CH Ref legal event code: PL |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: LI Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20090731 Ref country code: CH Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20090731 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: BE Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20090731 |
|
REG | Reference to a national code |
Ref country code: DE Ref legal event code: R082 Ref document number: 69732111 Country of ref document: DE Representative=s name: MIKULECKY, KLAUS, DIPL.-CHEM. DR.PHIL.NAT., DE Ref country code: DE Ref legal event code: R081 Ref document number: 69732111 Country of ref document: DE Owner name: CLARIANT INTERNATIONAL LTD, CH Free format text: FORMER OWNER: CLARIANT FINANCE (BVI) LTD., TORTOLA, VG |
|
REG | Reference to a national code |
Ref country code: FR Ref legal event code: PLFP Year of fee payment: 20 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: GB Payment date: 20160630 Year of fee payment: 20 Ref country code: ES Payment date: 20160518 Year of fee payment: 20 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: IT Payment date: 20160705 Year of fee payment: 20 Ref country code: DE Payment date: 20160715 Year of fee payment: 20 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: FR Payment date: 20160707 Year of fee payment: 20 |
|
REG | Reference to a national code |
Ref country code: DE Ref legal event code: R071 Ref document number: 69732111 Country of ref document: DE |
|
REG | Reference to a national code |
Ref country code: GB Ref legal event code: PE20 Expiry date: 20170702 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: GB Free format text: LAPSE BECAUSE OF EXPIRATION OF PROTECTION Effective date: 20170702 |
|
REG | Reference to a national code |
Ref country code: ES Ref legal event code: FD2A Effective date: 20180508 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: ES Free format text: LAPSE BECAUSE OF EXPIRATION OF PROTECTION Effective date: 20170704 |